Methods and system for redox flow battery idle state

ABSTRACT

Methods and systems are provided for a redox flow battery system. In one example, a method of operating a redox flow battery system includes, responsive to switching the redox flow battery system to an idle mode, initiating a first timer monitoring a first threshold period of time. An electrolyte pump may be activated when the first threshold period of time elapses, the electrolyte pump driving circulation of electrolytes through one or more electrode compartments.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. Utility applicationSer. No. 17/308,890, entitled “METHODS AND SYSTEM FOR REDOX FLOW BATTERYIDLE STATE,” and filed on May 5, 2021, which claims priority to U.S.Provisional Application No. 63/025,240, entitled “METHODS AND SYSTEM FORREDOX FLOW BATTERY IDLE STATE,” and filed on May 15, 2020. The entirecontents of the above-identified application are hereby incorporated byreference for all purposes.

FIELD

The present description relates generally to methods and systems for aredox flow battery.

BACKGROUND AND SUMMARY

Redox flow batteries are suitable for grid scale storage applicationsdue to their capability for scaling power and capacity independently, aswell as for charging and discharging over thousands of cycles withreduced performance losses in comparison to conventional batterytechnologies. An all-iron hybrid redox flow battery is particularlyattractive due to incorporation of low-cost, earth-abundant materials.Iron redox flow batteries (IFBs) rely on iron, salt, and water forelectrolyte, thus including simple, earth-abundant, and inexpensivematerials, and eliminating incorporation of harsh chemicals, therebyallowing the IFB to have a reduced impact on the environment.

However, the inventors herein have recognized potential issues with suchsystems. Namely, a redox flow battery in a charged state may lose energystorage capacity while sustaining idle mode much faster than atraditional battery in an analogous charged state (e.g., while similarlysustaining idle mode). In particular, redox flow battery systems maylose capacity by way of shunt current losses through the conductiveelectrolytes and from ionic movement through the membrane. Continuouslycycling fresh electrolyte to battery cells of the redox flow batterysystem, such as during idle operation of the redox flow battery, maymaintain such shunting losses at higher levels. Furthermore, the redoxflow battery system may suffer from parasitic power losses due tocontinuous pumping and heating of the electrolyte atcharging/discharging levels during the idle state, including pumpingparasitic loss and heating parasitic loss. Alternatively, periodic(e.g., as opposed to continuous) cycling of fresh electrolyte to thebattery cells may at least partially inhibit capacity loss in singlecell systems but may exacerbate shunting losses in larger batterymodules.

In one embodiment, the issues described above may be at least partiallyaddressed by a method of operating a redox flow battery system, themethod including, responsive to switching the redox flow battery systemto an idle mode, wherein the idle mode includes operation of the redoxflow battery system outside of a charging mode and outside of adischarging mode, completely draining electrolytes from one or moreelectrode compartments of the redox flow battery system, purging the oneor more electrode compartments with a gas, and refilling the one or moreelectrode compartments with fresh electrolytes. In this way, thetechnical effect can be achieved of maintaining a responsiveness of theredox flow battery system to charging and discharging commands while inthe idle mode, while reducing parasitic power losses due to pumping andheating, and reducing shunt current losses.

It should be understood that the summary above is provided to introducein simplified form a selection of concepts that are further described inthe detailed description. It is not meant to identify key or essentialfeatures of the claimed subject matter, the scope of which is defineduniquely by the claims that follow the detailed description.Furthermore, the claimed subject matter is not limited toimplementations that solve any disadvantages noted above or in any partof this disclosure.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a schematic of an example redox flow battery systemincluding a battery cell with electrodes and a membrane separator.

FIG. 2 shows a side view of an example layout for the redox flow batterysystem of FIG. 1 .

FIG. 3 shows a high level flow chart of an example method for operatingthe redox flow battery system of FIG. 1 .

FIG. 4 shows a first example method for operating the redox flow batterysystem of FIG. 1 in an idle mode.

FIG. 5 shows a second example method for operating the redox flowbattery system of FIG. 1 in the idle mode.

FIG. 6 shows a timeline plot illustrating operation of the redox flowbattery system of FIG. 1 in the idle mode.

FIG. 7 shows a graph comparing a battery state of charge during an idlemode with time.

DETAILED DESCRIPTION

The following description relates to systems and methods formanufacturing a redox flow battery with reduced cost of storage. Theredox flow battery is shown in FIG. 1 with an integrated multi-chambertank having separate positive and negative electrolyte chambers. In someexamples, the redox flow battery may be an all-iron flow battery (IFB)utilizing iron redox chemistry at both a negative electrode and apositive electrode of the IFB. The electrolyte chambers may be coupledto one or more battery cells, each cell including the negative electrodeand the positive electrode. The redox flow battery may be arranged in alayout including a housing and various other components as shown in aside view in FIG. 2 . An example of a method for operating the redoxflow battery is depicted in FIG. 3 . FIGS. 4 and 5 are examples ofmethods for operating the redox flow battery when the battery is in anidle mode. Adjustments to components of the redox flow battery duringoperation in the idle mode are depicted in FIG. 6 . Effects of themethods shown in FIGS. 4 and 5 on battery state of charge (SOC) areillustrated in FIG. 7 in a graph plotting SOC against time.

Hybrid redox flow batteries are redox flow batteries that arecharacterized by the deposition of one or more electroactive materialsas a solid layer on an electrode. Hybrid redox flow batteries may, forinstance, include a chemical that plates via an electrochemical reactionas a solid on a substrate throughout the battery charge process. Duringbattery discharge, the plated species may ionize via an electrochemicalreaction, becoming soluble in the electrolyte. In hybrid redox flowbattery systems, the charge capacity (e.g., a maximum amount of energystored) of the redox flow battery may be limited by the amount of metalplated during battery charge and may depend accordingly on theefficiency of the plating system as well as the available volume andsurface area available for plating.

As shown in FIG. 1 , in a redox flow battery system 10, a negativeelectrode 26 may be referred to as a plating electrode and a positiveelectrode 28 may be referred to as a redox electrode. A negativeelectrolyte within a plating side (e.g., a negative electrodecompartment 20) of a redox flow battery cell 18 may be referred to as aplating electrolyte, and a positive electrolyte on a redox side (e.g., apositive electrode compartment 22) of the redox flow battery cell 18 maybe referred to as a redox electrolyte.

“Anode” refers to the electrode where electroactive material loseselectrons and “cathode” refers to the electrode where electroactivematerial gains electrons. During battery charge, the negativeelectrolyte gains electrons at the negative electrode 26; therefore thenegative electrode 26 is the cathode of the electrochemical reaction.During discharge, the negative electrolyte loses electrons; thereforethe negative electrode 26 is the anode of the reaction. Alternatively,during discharge, the negative electrolyte and negative electrode 26 maybe respectively referred to as an anolyte and anode of theelectrochemical reaction, while the positive electrolyte and thepositive electrode 28 may be respectively referred to as a catholyte andcathode of the electrochemical reaction. During charge, the negativeelectrolyte and negative electrode 26 may be respectively referred to asthe catholyte and cathode of the electrochemical reaction, while thepositive electrolyte and the positive electrode 28 may be respectivelyreferred to as the anolyte and anode of the electrochemical reaction.For simplicity, the terms “positive” and “negative” are used herein torefer to the electrodes, electrolytes, and electrode compartments inredox battery flow systems.

One example of a hybrid redox flow battery is an all iron redox flowbattery (IFB), in which the electrolyte includes iron ions in the formof iron salts (e.g., FeCl₂, FeCl₃, and the like), wherein the negativeelectrode 26 includes metal iron. For example, at the negative electrode26, ferrous ion, Fe²⁺, receives two electrons and plates as iron metalonto the negative electrode 26 during battery charge, and iron metal,Fe⁰, loses two electrons and re-dissolves as Fe²⁺ during batterydischarge. At the positive electrode 28, Fe²⁺ loses an electron to formferric ion, Fe³⁺, during charge, and during discharge Fe³⁺ gains anelectron to form Fe²⁺. The electrochemical reaction is summarized inequations (1) and (2), wherein the forward reactions (left to right)indicate electrochemical reactions during battery charge, while thereverse reactions (right to left) indicate electrochemical reactionsduring battery discharge:

Fe²⁺+2e ⁻↔Fe⁰ −0.44 V (negative electrode)   (1)

Fe²⁺↔2Fe³⁺+2e ⁻ +0.77 V (positive electrode)   (2)

As discussed above, the negative electrolyte used in the IFB may providea sufficient amount of Fe²⁺ so that, during charge, Fe²⁺ can accept twoelectrons from the negative electrode 26 to form Fe⁰ and plate onto asubstrate. During discharge, the plated Fe⁰ may then lose two electrons,ionizing into Fe²⁺ and may be dissolved back into the electrolyte. Theequilibrium potential of the above reaction is −0.44 V and thus, thisreaction provides a negative terminal for the desired system. On thepositive side of the IFB, the electrolyte may provide Fe²⁺ during chargewhich loses an electron and oxidizes to Fe³⁺. During discharge, Fe³⁺provided by the electrolyte becomes Fe²⁺ by absorbing an electronprovided by the positive electrode 28. The equilibrium potential of thisreaction is +0.77 V, creating a positive terminal for the desiredsystem.

The IFB provides the ability to charge and recharge its electrolytes incontrast to other battery types utilizing non-regenerating electrolytes.Charge is achieved by applying a current across the electrodes 26 and 28via terminals 40 and 42, respectively. The negative electrode 26 may beelectrically coupled via terminal 40 to the negative side of a voltagesource so that electrons may be delivered to the negative electrolytevia the positive electrode 28 (e.g., as Fe²⁺ is oxidized to Fe³⁺ in thepositive electrolyte in the positive electrode compartment 22). Theelectrons provided to the negative electrode 26 (e.g., platingelectrode) can reduce the Fe²⁺ in the negative electrolyte to form Fe⁰at the plating substrate, causing it to plate onto the negativeelectrode 26.

Discharge can be sustained while Fe⁰ remains available to the negativeelectrolyte for oxidation and while Fe³⁺ remains available in thepositive electrolyte for reduction. As an example, Fe³⁺ availability canbe maintained by increasing the concentration or the volume of thepositive electrolyte to the positive electrode compartment 22 side ofthe redox flow battery cell 18 to provide additional Fe³⁺ ions via anexternal source, such as an external positive electrolyte chamber 52.More commonly, availability of Fe⁰ during discharge may be an issue inIFB systems, wherein the Fe⁰ available for discharge may be proportionalto the surface area and volume of the negative electrode substrate aswell as the plating efficiency. Charge capacity may be dependent on theavailability of Fe²⁺ in the negative electrode compartment 20. As anexample, Fe²⁺ availability can be maintained by providing additionalFe²⁺ ions via an external source, such as an external negativeelectrolyte chamber 50 to increase the concentration or the volume ofthe negative electrolyte to the negative electrode compartment 20 sideof the redox flow battery cell 18.

In an IFB, the positive electrolyte includes ferrous ions, ferric ions,ferric complexes, or any combination thereof, while the negativeelectrolyte includes ferrous ions or ferrous complexes, depending on theSOC of the IFB system. As previously mentioned, utilization of iron ionsin both the negative electrolyte and the positive electrolyte allows forutilization of the same electrolytic species on both sides of the redoxflow battery cell 18, which can reduce electrolyte cross-contaminationand can increase the efficiency of the IFB system, resulting in lesselectrolyte replacement as compared to other redox flow battery systems.

Efficiency losses in an IFB may result from electrolyte crossoverthrough a separator 24 (e.g., ion-exchange membrane barrier, microporousmembrane, and the like). For example, ferric ions in the positiveelectrolyte may be driven toward the negative electrolyte by a ferricion concentration gradient and an electrophoretic force across theseparator 24. Subsequently, ferric ions penetrating the separator 24(e.g., the membrane barrier) and crossing over to the negative electrodecompartment 20 may result in coulombic efficiency losses. Ferric ionscrossing over from the low pH redox side (e.g., more acidic positiveelectrode compartment 22) to high pH plating side (e.g., less acidicnegative electrode compartment 20) may result in precipitation ofFe(OH)₃. Precipitation of Fe(OH)₃ may degrade the separator 24 and causepermanent battery performance and efficiency losses. For example,Fe(OH)₃ precipitate may chemically foul the organic functional group ofan ion-exchange membrane or physically clog the small micropores of anion-exchange membrane. In either case, due to the Fe(OH)₃ precipitate,membrane ohmic resistance may rise over time and battery performance maydegrade. Precipitate may be removed by washing the battery with acid,but the constant maintenance and downtime may be disadvantageous forcommercial battery applications. Furthermore, washing may be dependenton regular preparation of electrolyte, contributing to additionalprocessing costs and complexity. Alternatively, adding specific organicacids to the positive electrolyte and the negative electrolyte inresponse to electrolyte pH changes may mitigate precipitate formationduring battery charge and discharge cycling without driving up overallcosts. Additionally, implementing a membrane barrier that inhibitsferric ion crossover may also mitigate fouling.

Additional coulombic efficiency losses may be caused by reduction of H⁺(e.g., protons) and subsequent formation of H₂ (e.g., hydrogen gas), andthe reaction of protons in the negative electrode compartment 20 withelectrons supplied at the plated iron metal of the negative electrode 26to form hydrogen gas.

The IFB electrolyte (e.g., FeCl₂, FeCl₃, FeSO₄, Fe₂(SO₄)₃, and the like)is readily available and can be produced at low costs. The IFBelectrolyte offers higher reclamation value because the same electrolytecan be used for the negative electrolyte and the positive electrolyte,consequently reducing cross contamination issues as compared to othersystems. Furthermore, owing to its electron configuration, iron maysolidify into a generally uniform solid structure during plating thereofon the negative electrode substrate. For zinc and other metals commonlyused in hybrid redox batteries, solid dendritic structures may formduring plating. The stable electrode morphology of the IFB system mayincrease the efficiency of the battery in comparison to other redox flowbatteries. Further still, iron redox flow batteries reduce the use oftoxic raw materials and can operate at a relatively neutral pH ascompared to other redox flow battery electrolytes. Accordingly, IFBsystems reduce environmental hazards as compared with all other currentadvanced redox flow battery systems in production.

Continuing with FIG. 1 , a schematic illustration of the redox flowbattery system 10 is shown. The redox flow battery system 10 may includethe redox flow battery cell 18 fluidly connected to an integratedmulti-chambered electrolyte storage tank 110. The redox flow batterycell 18 may generally include the negative electrode compartment 20,separator 24, and positive electrode compartment 22. The separator 24may include an electrically insulating ionic conducting barrier whichprevents bulk mixing of the positive electrolyte and the negativeelectrolyte while allowing conductance of specific ions therethrough.For example, the separator 24 may include an ion-exchange membraneand/or a microporous membrane.

The negative electrode compartment 20 may include the negative electrode26, and the negative electrolyte may include electroactive materials.The positive electrode compartment 22 may include the positive electrode28, and the positive electrolyte may include electroactive materials. Insome examples, multiple redox flow battery cells 18 may be combined inseries or in parallel to generate a higher voltage or current in theredox flow battery system 10.

Further illustrated in FIG. 1 are the negative and positive electrolytepumps 30 and 32, both used to pump electrolyte solution through theredox flow battery system 10. Electrolytes are stored in one or moretanks external to the cell, and are pumped via the negative and positiveelectrolyte pumps 30 and 32 through the negative electrode compartment20 side and the positive electrode compartment 22 side of the redox flowbattery cell 18, respectively.

The redox flow battery system 10 may also include a first bipolar plate36 and a second bipolar plate 38, each positioned along a rear-facingside, e.g., opposite of a side facing the separator 24, of the negativeelectrode 26 and the positive electrode 28, respectively. The firstbipolar plate 36 may be in contact with the negative electrode 26 andthe second bipolar plate 38 may be in contact with the positiveelectrode 28. In other examples, however, the bipolar plates 36 and 38may be arranged proximate but spaced away from the electrodes 26 and 28within the respective electrode compartments 20 and 22. In either case,the bipolar plates 36 and 38 may be electrically coupled to theterminals 40 and 42, respectively, either via direct contact therewithor through the negative and positive electrodes 26 and 28, respectively.The IFB electrolytes may be transported to reaction sites at thenegative and positive electrodes 26 and 28 by the first and secondbipolar plates 36 and 38, resulting from conductive properties of amaterial of the bipolar plates 36, 38. Electrolyte flow may also beassisted by the negative and positive electrolyte pumps 30 and 32,facilitating forced convection through the redox flow battery cell 18.Reacted electrochemical species may also be directed away from thereaction sites by the combination of forced convection and the presenceof the first and second bipolar plates 36 and 38.

As illustrated in FIG. 1 , the redox flow battery cell 18 may furtherinclude negative battery terminal 40 and positive battery terminal 42.When a charge current is applied to the battery terminals 40 and 42, thepositive electrolyte is oxidized (lose one or more electrons) at thepositive electrode 28, and the negative electrolyte is reduced (gain oneor more electrons) at the negative electrode 26. During batterydischarge, reverse redox reactions occur on the electrodes 26 and 28. Inother words, the positive electrolyte is reduced (gains one or moreelectrons) at the positive electrode 28, and the negative electrolyte isoxidized (loses one or more electrons) at the negative electrode 26. Theelectrical potential difference across the battery is maintained by theelectrochemical redox reactions in the positive electrode compartment 22and the negative electrode compartment 20, and may induce a currentthrough a current collector while the reactions are sustained. Theamount of energy stored by a redox battery is limited by the amount ofelectro-active material available in electrolytes for discharge,depending on the total volume of electrolytes and the solubility of theelectroactive materials.

The redox flow battery system 10 may further include the integratedmulti-chambered electrolyte storage tank 110. The multi-chamberedelectrolyte storage tank 110 may be divided by a bulkhead 98. Thebulkhead 98 may create multiple chambers within the multi-chamberedelectrolyte storage tank 110 so that both the positive and negativeelectrolytes may be included within a single tank. The negativeelectrolyte chamber 50 holds negative electrolyte includingelectroactive materials, and the positive electrolyte chamber 52 holdspositive electrolyte including electroactive materials. The bulkhead 98may be positioned within the multi-chambered electrolyte storage tank110 to yield a desired volume ratio between the negative electrolytechamber 50 and the positive electrolyte chamber 52. In one example, thebulkhead 98 may be positioned to set the volume ratio of the negativeand positive electrolyte chambers 50 and 52 according to thestoichiometric ratio between the negative and positive redox reactions.FIG. 1 further illustrates fill height 112 of the multi-chamberedelectrolyte storage tank 110, which may indicate the liquid level ineach tank compartment. FIG. 1 also shows gas head space 90 located abovethe fill height 112 of negative electrolyte chamber 50, and gas headspace 92 located above the fill height 112 of positive electrolytechamber 52. The gas head space 92 may be utilized to store hydrogen gasgenerated through operation of the redox flow battery (e.g., due toproton reduction and corrosion side reactions) and conveyed to themulti-chambered electrolyte storage tank 110 with returning electrolytefrom the redox flow battery cell 18. The hydrogen gas may be separatedspontaneously at the gas-liquid interface (e.g., fill height 112) withinthe multi-chambered electrolyte storage tank 110, thereby precludinghaving additional gas-liquid separators as part of the redox flowbattery system 10. Once separated from the electrolyte, the hydrogen gasmay fill the gas head spaces 90 and 92. As such, the stored hydrogen gascan aid in purging other gases from the multi-chambered electrolytestorage tank 110, thereby acting as an inert gas blanket for reducingoxidation of electrolyte species, which can help to reduce redox flowbattery capacity losses. In this way, utilizing the integratedmulti-chambered electrolyte storage tank 110 may forego having separatenegative and positive electrolyte storage tanks, hydrogen storage tanks,and gas-liquid separators common to conventional redox flow batterysystems, thereby simplifying the system design, reducing the physicalfootprint of the redox flow battery system 10, and reducing systemcosts.

In one example, the gas head spaces 90, 92 of the integratedmulti-chambered electrolyte storage tank 110 may be coupled to a gasstorage tank 102, siphoning accumulated hydrogen to the gas storage tank102. During periods when the redox flow battery system 10 is switched toan idle mode, the positive and negative electrode compartments 22, 20may be intermittently drained. For example, valves (not shown at FIG. 1) controlling flow of electrolyte between the electrode compartments 20,22 and the integrated multi-chambered electrolyte storage tank 110 maybe opened and the electrolyte in the electrode compartments 20, 22 maybe pumped out of the electrode compartments 20, 22. The electrodecompartments 20, 22 may then be flushed under an oxygen-free environmentby purging the empty electrode compartments 20, 22 with a gas such asthe hydrogen delivered from the gas head spaces 90, 92 of the integratedmulti-chambered electrolyte storage tank 110 via the gas storage tank102. In some examples, the gas storage tank 102 may not be coupled tothe integrated multi-chambered electrolyte storage tank 110. Instead,the gas storage tank 102 may be an independent tank of hydrogen gas orargon gas. Either hydrogen or argon gas may be used to flush theelectrode compartments 20, 22 to reduce a likelihood of performanceand/or capacitance loss while the redox flow battery system 10 is in theidle mode. Details of methods for the redox flow battery system 10during the idle mode are described further below with reference to FIGS.3-5 .

FIG. 1 also shows spillover hole 96, which creates an opening in thebulkhead 98 between gas head spaces 90 and 92, and provides a means ofequalizing gas pressure between the two chambers 50, 52. The spilloverhole 96 may be positioned a threshold height above the fill height 112.The spillover hole 96 further enables a capability to self-balance theelectrolytes in each of the positive and negative electrolyte chambers50 and 52 in the event of a battery crossover. In the case of anall-iron redox flow battery system, the same electrolyte (Fe²⁺) is usedin both negative and positive electrode compartments 20 and 22, sospilling over of electrolyte between the negative and positiveelectrolyte chambers 50 and 52 may reduce overall system efficiency, butthe overall electrolyte composition, battery module performance, andbattery module capacity are maintained. Flange fittings may be utilizedfor all piping connections for inlets and outlets to and from themulti-chambered electrolyte storage tank 110 to maintain a continuouslypressurized state without leaks. The multi-chambered electrolyte storagetank 110 can include at least one outlet from each of the negative andpositive electrolyte chambers 50 and 52, and at least one inlet to eachof the negative and positive electrolyte chambers 50 and 52.Furthermore, one or more outlet connections may be provided from the gashead spaces 90 and 92 for directing hydrogen gas to rebalancing reactors80 and 82.

Although not shown in FIG. 1 , integrated multi-chambered electrolytestorage tank 110 may further include one or more heaters thermallycoupled to each of the negative electrolyte chamber 50 and the positiveelectrolyte chamber 52. In alternate examples, only one of the negativeand positive electrolyte chambers 50 and 52 may include one or moreheaters. In the case where only the positive electrolyte chamber 52includes one or more heaters, the negative electrolyte may be heated bytransferring heat generated at the redox flow battery cell(s) 18 of apower module (e.g., power module 210, as discussed in detail below withreference to FIG. 2 ) to the negative electrolyte. In this way, theredox flow battery cell(s) 18 of the power module may heat andfacilitate temperature regulation of the negative electrolyte. The oneor more heaters may be actuated by controller 88 to regulate atemperature of the negative electrolyte chamber 50 and the positiveelectrolyte chamber 52 independently or together. For example, inresponse to an electrolyte temperature decreasing below a thresholdtemperature, the controller 88 may increase a power supplied to one ormore heaters so that a heat flux to the electrolyte is increased. Theelectrolyte temperature may be indicated by one or more temperaturesensors mounted at the multi-chambered electrolyte storage tank 110,including sensors 60 and 62. As examples, the one or more heaters mayinclude coil type heaters or other immersion heaters immersed in theelectrolyte fluid, or surface mantle type heaters that transfer heatconductively through the walls of the negative and positive electrolytechambers 50 and 52 to heat the fluid therein. Other known types of tankheaters may be employed without departing from the scope of the presentdisclosure. Furthermore, controller 88 may deactivate one or moreheaters in the negative and positive electrolyte chambers 50, 52 inresponse to a liquid level decreasing below a solids fill thresholdlevel. Said in another way, controller 88 may activate the one or moreheaters in the negative and positive electrolyte chambers 50, 52 only inresponse to a liquid level increasing above the solids fill thresholdlevel. In this way, activating the one or more heaters withoutsufficient liquid in the positive and/or negative electrolyte chambers52, 50 can be averted, thereby reducing a risk of overheating or burningout the heater(s).

Further still, one or more inlet connections may be provided to each ofthe negative and positive electrolyte chambers 50, 52 from a fieldhydration system (not shown). In this way, the field hydration systemcan facilitate commissioning of the redox flow battery system 10,including installing, filling, and hydrating the redox flow batterysystem 10, at an end-use location. Furthermore, prior to itscommissioning at the end-use location, the redox flow battery system 10may be dry-assembled at a battery manufacturing facility different fromthe end-use location without filling and hydrating the redox flowbattery system 10, before delivering the redox flow battery system 10 tothe end-use location. In one example, the end-use location maycorrespond to the location where the redox flow battery system 10 is tobe installed and utilized for on-site energy storage. Said in anotherway, it is anticipated that, once installed and hydrated at the end-uselocation, a position of the redox flow battery system 10 becomes fixed,and the redox flow battery system 10 is no longer deemed a portable, drysystem. Thus, from the perspective of a redox flow battery systemend-user, the dry portable redox flow battery system 10 may be deliveredon-site, after which the redox flow battery system 10 is installed,hydrated, and commissioned. Prior to hydration the redox flow batterysystem 10 may be referred to as a dry, portable system, the redox flowbattery system 10 being free of or without water and wet electrolyte.Once hydrated, the redox flow battery system 10 may be referred to as awet non-portable system, the redox flow battery system 10 including wetelectrolyte.

Further illustrated in FIG. 1 , electrolyte solutions typically storedin the multi-chambered electrolyte storage tank 110 are pumped vianegative and positive electrolyte pumps 30 and 32 throughout the redoxflow battery system 10. Electrolyte stored in negative electrolytechamber 50 is pumped via negative electrolyte pump 30 through thenegative electrode compartment 20 side of the redox flow battery cell18, and electrolyte stored in positive electrolyte chamber 52 is pumpedvia positive electrolyte pump 32 through the positive electrodecompartment 22 side of the redox flow battery cell 18.

Two electrolyte rebalancing reactors 80 and 82, may be connected in-lineor in parallel with the recirculating flow paths of the electrolyte atthe negative and positive sides of the redox flow battery cell 18,respectively, in the redox flow battery system 10. One or morerebalancing reactors may be connected in-line with the recirculatingflow paths of the electrolyte at the negative and positive sides of thebattery, and other rebalancing reactors may be connected in parallel,for redundancy (e.g., a rebalancing reactor may be serviced withoutdisrupting battery and rebalancing operations) and for increasedrebalancing capacity. In one example, the electrolyte rebalancingreactors 80 and 82 may be placed in the return flow path from thenegative and positive electrode compartments 20 and 22 to the negativeand positive electrolyte chambers 50 and 52, respectively. Electrolyterebalancing reactors 80 and 82 may serve to rebalance electrolyte chargeimbalances in the redox flow battery system 10 occurring due to sidereactions, ion crossover, and the like, as described herein. In oneexample, electrolyte rebalancing reactors 80 and 82 may include tricklebed reactors, where the hydrogen gas and electrolyte are contacted atcatalyst surfaces in a packed bed for carrying out the electrolyterebalancing reaction. In other examples the rebalancing reactors 80 and82 may include flow-through type reactors that are capable of contactingthe hydrogen gas and the electrolyte liquid and carrying out therebalancing reactions in the absence of a packed catalyst bed.

During operation of the redox flow battery system 10, sensors and probesmay monitor and control chemical properties of the electrolyte such aselectrolyte pH, concentration, SOC, and the like. For example, asillustrated in FIG. 1 , sensors 62 and 60 maybe be positioned to monitorpositive electrolyte and negative electrolyte conditions at the positiveelectrolyte chamber 52 and the negative electrolyte chamber 50,respectively. In another example, sensors 62 and 60 may each include oneor more electrolyte level sensors to indicate a level of electrolyte inthe positive electrolyte chamber 52 and the negative electrolyte chamber50, respectively. As another example, sensors 72 and 70, alsoillustrated in FIG. 1 , may monitor positive electrolyte and negativeelectrolyte conditions at the positive electrode compartment 22 and thenegative electrode compartment 20, respectively. The sensors 72, 70 maybe pH probes, optical probes, pressure sensors, voltage sensors, etc.Sensors may be positioned at other locations throughout the redox flowbattery system 10 to monitor electrolyte chemical properties and otherproperties.

For example, a sensor may be positioned in an external acid tank (notshown) to monitor acid volume or pH of the external acid tank, whereinacid from the external acid tank is supplied via an external pump (notshown at FIG. 1 ) to the redox flow battery system 10 in order to reduceprecipitate formation in the electrolytes. Additional external tanks andsensors may be installed for supplying other additives to the redox flowbattery system 10. For example, various sensors including, temperature,conductivity, and level sensors of a field hydration system may transmitsignals to the controller 88. Furthermore, controller 88 may sendsignals to actuators such as valves and pumps of the field hydrationsystem during hydration of the redox flow battery system 10. Sensorinformation may be transmitted to a controller 88 which may in turnactuate pumps 30 and 32 to control electrolyte flow through the redoxflow battery cell 18, or to perform other control functions, as anexample. In this manner, the controller 88 may be responsive to, one ora combination of sensors and probes.

Redox flow battery system 10 may further include a source of hydrogengas. In one example the source of hydrogen gas may include a separatededicated hydrogen gas storage tank. In the example of FIG. 1 , hydrogengas may be stored in and supplied from the integrated multi-chamberedelectrolyte storage tank 110. Integrated multi-chambered electrolytestorage tank 110 may supply additional hydrogen gas to the positiveelectrolyte chamber 52 and the negative electrolyte chamber 50.Integrated multi-chambered electrolyte storage tank 110 may alternatelysupply additional hydrogen gas to the inlet of electrolyte rebalancingreactors 80 and 82. As an example, a mass flow meter or other flowcontrolling device (which may be controlled by controller 88) mayregulate the flow of the hydrogen gas from integrated multi-chamberedelectrolyte storage tank 110. The integrated multi-chambered electrolytestorage tank 110 may supplement the hydrogen gas generated in redox flowbattery system 10. For example, when gas leaks are detected in redoxflow battery system 10 or when the reduction reaction rate is too low atlow hydrogen partial pressure, hydrogen gas may be supplied from theintegrated multi-chambered electrolyte storage tank 110 or the gasstorage tank 102 in order to rebalance the SOC of the electroactivespecies in the positive electrolyte and negative electrolyte. As anexample, controller 88 may supply hydrogen gas from integratedmulti-chambered electrolyte storage tank 110 or the gas storage tank 102in response to a measured change in pH or in response to a measuredchange in SOC of an electrolyte or an electroactive species.

For example, an increase in pH of the negative electrolyte chamber 50,or the negative electrode compartment 20, may indicate that hydrogen isleaking from the redox flow battery system 10 and/or that the reactionrate is too slow with the available hydrogen partial pressure, andcontroller 88, in response to the pH increase, may increase a supply ofhydrogen gas from integrated multi-chambered electrolyte storage tank110 to the redox flow battery system 10. As a further example,controller 88 may supply hydrogen gas from integrated multi-chamberedelectrolyte storage tank 110 in response to a pH change, wherein the pHincreases beyond a first threshold pH or decreases beyond a secondthreshold pH. In the case of an IFB, controller 88 may supply additionalhydrogen to increase the rate of reduction of ferric ions and the rateof production of protons, thereby reducing the pH of the positiveelectrolyte. Furthermore, the negative electrolyte pH may be lowered byhydrogen reduction of ferric ions crossing over from the positiveelectrolyte to the negative electrolyte or by protons, generated at thepositive side, crossing over to the negative electrolyte due to a protonconcentration gradient and electrophoretic forces. In this manner, thepH of the negative electrolyte may be maintained within a stable region,while reducing the risk of precipitation of ferric ions (crossing overfrom the positive electrode compartment 22) as Fe(OH)₃.

Other control schemes for controlling the supply rate of hydrogen gasfrom integrated multi-chambered electrolyte storage tank 110 responsiveto a change in an electrolyte pH or to a change in an electrolyte SOC,detected by other sensors such as an oxygen-reduction potential (ORP)meter or an optical sensor, may be implemented. Further still, thechange in pH or SOC triggering the action of controller 88 may be basedon a rate of change or a change measured over a time period. The timeperiod for the rate of change may be predetermined or adjusted based onthe time constants for the redox flow battery system 10. For example,the time period may be reduced if the recirculation rate is high, andlocal changes in concentration (e.g., due to side reactions or gasleaks) may quickly be measured since the time constants may be small.

Turning now to FIG. 2 , it illustrates a side view of an example redoxflow battery system layout 200 for the redox flow battery system 10.Redox flow battery system layout 200 may be housed within a housing 202that facilitates long-distance transport and delivery of the redox flowbattery system 10. In some examples, the housing 202 can include astandard steel freight container or a freight trailer that can betransported via rail, truck or ship. The redox flow battery systemlayout 200 can include the integrated multi-chambered electrolytestorage tank 110 and one or more rebalancing reactors (e.g., rebalancingreactor 80) positioned at a first side of the housing 202, and a powermodule 210, and power control system (PCS) 288 at a second side of thehousing 202. Auxiliary components such as supports 206, as well asvarious piping 204, pumps 230, valves (not shown at FIG. 2 ), and thelike may be included within the housing 202 (as further described abovewith reference to FIG. 1 ) for stabilizing and fluidly connecting thevarious components positioned therein. For example, one or more pumps230 may be utilized to convey electrolyte from the integratedmulti-chambered electrolyte storage tank 110 to one or more redox flowbattery cell stacks 214 within the power module 210. Furthermore,additional pumps 230 may be utilized to return electrolyte from thepower module 210 to the negative electrolyte chamber 50 or the positiveelectrolyte chamber 52 of the integrated multi-chambered electrolytestorage tank 110.

Power module 210 may include one or more redox flow battery cell stacks214 electrically connected in parallel and/or in series. Each of the oneor more redox flow battery cell stacks 214 may further include aplurality of redox flow battery cells 18 connected in parallel and/orseries. In this way, power module 210 may be able to supply a range ofcurrent and/or voltages to external loads. The PCS 288 includescontroller 88 of FIG. 1 , as well as other electronics, for controllingand monitoring operation of the redox flow battery system 10.Furthermore, PCS 288 may regulate and monitor voltage supplied toexternal loads, as well as supplying current and/or voltage fromexternal sources for charging of the power module 210. The PCS 288 mayfurther regulate and control operation of the redox flow battery system10 during an idle state or idle mode. The redox flow battery system 10being in an idle state may include when the power module 210 is not incharge mode or discharge mode. As an example, the power module 210 maybe in charge mode when an external voltage or current is supplied to oneor more redox flow battery cells 18 of the power module 210 resulting inreduction of electrolyte and plating of the reduced electrolyte at thenegative electrode(s) of the one or more redox flow battery cells 18.For the case of an IFB, ferrous ions may be reduced at the platingelectrode(s) of one or more redox flow battery cells 18, thereby platingiron thereat during charging of the power module 210. As anotherexample, the power module 210 may be in a discharge mode when voltage orcurrent is supplied from one or more redox flow battery cells 18 of thepower module 210 resulting in oxidation of plated metal at the negativeelectrode resulting in deplating (e.g., loss of metal) and solubilizingof the oxidized metal ions. For the case of an IFB, iron may be oxidizedat the plating electrode of one or more redox flow battery cells 18,thereby solubilizing ferrous ions thereat during discharging of thepower module 210. Further details regarding conditions for entering andexiting the battery charge and discharge modes of the redox flow batterysystem 10 are described with reference to FIGS. 3-5 below.

Turning now to FIGS. 3-5 , they show flow charts for method 300, 400,and 500, respectively, for operating a redox flow battery system, suchas the redox flow battery system 10 of FIGS. 1 and 2 . Instructions forcarrying out methods 300, 400, and 500 may reside onboard and beexecuted by a controller, such as controller 88 of FIG. 1 . For example,the executable instructions may be stored in non-transitory memoryonboard the controller and may be executed in conjunction with signalsreceived from sensors of redox flow battery system, such as the sensorsdescribed above with reference to FIG. 1 . The controller may furtheremploy actuators including pumps, valves, heaters, and the like, asdescribed above with reference to FIG. 1 , of the redox flow batterysystem to adjust battery operation, according to the methods describedbelow.

Method 300 includes a method for determining when the redox flow batterysystem may be in a charging, discharging, or idle mode. The method 300may begin at 302, where the method includes determining, estimating,and/or measuring current battery operating parameters. Current batteryoperating parameters may include, but are not limited to, one or more ofbattery SOC, power (including current and voltage) supplied to the powermodule, power (including current and voltage) supplied by the powermodule, internal power demand set points, and external power demand setpoints, and the like.

At 304, the method 300 includes determining if a power set point of theredox flow battery system is greater than zero, e.g., a positive value.The power set point may be an amount of power measured at a powermodule, e.g., the power module 210 of FIG. 2 , of the redox flow batterysystem. The power set point may be greater than zero when battery cellsof the power module are receiving a current or voltage from an externalsource. If the power set point is detected to be greater than zero, theredox flow battery system is determined to be in a charging mode at 306and the method 300 returns.

In one example, the redox flow battery system may be in the chargingmode when a system DC voltage is lower than a microgrid DC bus voltage.In response, the redox flow battery system may be configured toautomatically adjust to the charging mode to maintain the bus voltage.

If the power set point is not greater than zero, the method 300continues to 308 to evaluate if the power set point is less than zero,e.g., a negative value. The power set point may be less than zero whenbattery cells of the power module are supplying a current or voltage toan external source. If the power set point is detected to be less thanzero, the redox flow battery system is determined to be in a dischargingmode at 310 and the method 300 returns.

In one example, the redox flow battery system may be in the dischargingmode when the system DC voltage is higher than the microgrid DC busvoltage. The redox flow battery system may be configured toautomatically adjust to the discharging mode to maintain the busvoltage.

If the power set point is not less than zero, the power set point isdeemed to be equal to zero. The method 300 proceeds to 312 to adjust theredox flow battery system to an idle mode. A method 400 for the idlemode of the redox flow battery system is shown in FIG. 4 .

Turning now to FIG. 4 , it shows the method 400 for idling a redox flowbattery system that can aid in lowering system capacity losses. Method400 includes adjusting a pump ON/OFF status based on a time elapsedbetween pump activation cycles during idle mode of the redox flowbattery system. Method 400 may begin following 312 of method 300 of FIG.3 , when the redox flow battery system enters idle mode.

The method 400 may begin at 402, where the controller 88 may estimateand/or measure operating parameters of the redox flow battery system. Asdescribed above at 302 of FIG. 3 , the controller 88 may determine oneor more of battery SOC, power module voltage, pump activity (e.g.,electrolyte pump ON/OFF statuses, electrolyte pump flow rates, pumptimers, and the like), electrolyte temperatures, power (includingcurrent and voltage) supplied to the power module, power (includingcurrent and voltage) supplied by the power module, internal power demandset points, and external power demand set points, and the like. Variousoperating parameters may be indicated by one or more sensors of theredox flow battery system.

At 404, in response to the redox flow battery system being in idle mode,the method 400 includes deactivating power electronics. Powerelectronics may include one or more of a DC/DC converter, DC/ACinverter, and a power module contactor. Deactivating power electronicsmay aid in reducing power consumption of the redox flow battery systemwhile in idle mode. Deactivating the power electronics may include acontroller signaling to one or more actuators of the redox flow batterysystem to power OFF, which may inhibit an ability of the redox flowbattery system to discharge and/or charge. Deactivating the powerelectronics may include a mechanical switch that a user may set in idlemode. Additionally, deactivating power electronics may include displayof a message at a human machine interface (HMI) to alert a user that theredox flow battery system is in (or initiating) the idle mode.Furthermore, the display of the HMI may be dimmed or put in sleep mode,thereby reducing an illumination emitted therefrom.

Next, at 406, in response to the redox flow battery system being in idlemode, the controller 88 may reduce the electrolyte temperature in orderto further reduce power consumption while operating in idle mode.Reducing electrolyte temperature also may aid in reducing overall heatlosses to the environment during idle mode due to lower temperaturegradients between the redox flow battery system and the surroundingambient atmosphere. In one example, reducing the electrolyte temperaturemay include adjusting a heater set point based on the redox flow batterysystem being in idle mode. For example, the controller 88 may send acontrol signal to one or more heater actuators to reduce an electrolytetemperature below an idle threshold temperature. The one or more heatersmay be thermally coupled to the negative and positive electrodecompartments 20 and 22, and/or the negative and positive electrolytechambers 50 and 52 of the multi-chambered electrolyte storage tank 110(see FIG. 1 ). Adjusting a heater set point may further include reducinga heater output power set point to reduce heater output power in orderto reduce the electrolyte temperature below the idle thresholdtemperature. The idle threshold temperature may be based on a solubilityor stability of the electrolytes during idle mode. For example, belowthe idle threshold temperature, a risk of destabilization of theelectrolyte may be increased; destabilization of the electrolyte mayinclude precipitation of electrolyte salts, which reduces the redox flowbattery system capacity and performance. Such destabilization may beconsidered less problematic during idle mode than during battery chargeand discharge modes, though switching from idle mode to battery chargeor discharge mode may take longer (e.g., while the electrolytere-stabilizes). In contrast, above the idle threshold temperature, arisk of destabilization of the electrolyte is reduced and electrolytestability can be maintained without precipitation of any electrolytesalts. The relationship between electrolyte solubility, the idlethreshold temperature, and the control signal (e.g., heater outputpower) for the one or more heaters may be predetermined or otherwiseempirically determined for a particular redox flow battery system.

In another example, reducing the electrolyte temperature may include thecontroller 88 adjusting a control signal to one or more heaters todecrease a heater set point in order to decrease the electrolytetemperature during idle mode relative to an electrolyte temperatureduring battery charge and discharge modes. In one example, lowering aheater output power during idle mode may cool or lower an amount of heattransferred from the one or more heaters to the electrolyte relative tothe amount of heat transferred from the one or more heaters to theelectrolyte during battery charge and discharge modes. A temperature ofa redox flow battery system during battery charge and discharge modesmay be substantially equal to 60° C., in one example. However, duringidle mode, the heater setting may be decreased to maintain redox flowbattery system to an idle threshold temperature equivalent to an ambientor room temperature range between 25-30° C.

At 408, in response to the redox flow battery system being in the idlemode, the controller 88 begins cycling of the electrolyte pump(s),including deactivating the electrolyte pump and initiating a firsttimer, timer 1, and a second timer, timer 2. The first timer may be usedto indicate an elapsed time since one or more electrolyte pumps havebeen deactivated. Deactivating the electrolyte pump may include turningoff the electrolyte pump, wherein the pump may remain dormant while theredox flow battery system may be maintained in a state (e.g., SOCgreater than a threshold SOC) where the redox flow battery system canreadily provide a desired power output promptly upon receiving a powerrequest. In one example, deactivating the one or more electrolyte pumpsmay include deactivating pumps 30 and/or 32 of FIG. 1 . In otherexamples, deactivating the one or more electrolyte pumps may includedeactivating a sufficient number of pumps such that circulation ofelectrolyte to and from the redox flow battery cells is stopped. Infurther examples, deactivating the one or more electrolyte pumps mayinclude deactivating a sufficient number of pumps such that circulationof electrolyte to and from the redox flow battery cells is reduced belowa deactivation threshold flow rate.

In this way, an electrolyte flow rate and pumping of electrolytes fromthe multi-chambered electrolyte storage tank 110 to the negative andpositive electrolyte chambers 50 and 52 of one or more redox flowbattery cells 18 may be stopped or maintained at the deactivationthreshold flow rate. In one example, the deactivation threshold flowrate may correspond to a flow rate below which shunting losses aresubstantially reduced since the supply of fresh electrolyte to the redoxflow battery cells is reduced. In another example, the deactivationthreshold flow rate may correspond to a zero flow rate, and shutting offthe electrolyte pump. In some cases, having a non-zero deactivation flowrate may help to preserve a life of the electrolyte pump, by avoidingcompletely shutting the pump off. Stopping the electrolyte flow and/orreducing the flow of electrolyte to the deactivation threshold flow rateduring idle mode can aid in reducing shunt losses conducted through theflowing electrolytes since the amount of fresh electrolyte supplied tothe redox flow battery cells is reduced. Furthermore, shunt currentlosses may be confined to the existing volume of electrolyte within thepower module when the pumps are deactivated, including operating belowthe deactivation threshold flow rate. Having a lower concentration offresh electrolyte in the redox flow battery cells during idle mode canreduce a driving force for current shunt losses through the electrolyte.Furthermore, cycling the electrolyte pumps, including deactivating theelectrolyte pumps at 408, can aid in reducing parasitic pump powerlosses.

At 409, the controller 88 may include measuring the first timer, anddetermining a duration for which one or more of the electrolyte pumpswas deactivated. At 410, the controller 88 may determine if the firsttimer is greater than a first threshold duration. The first thresholdduration may be based on a target amount of time between successiveactivation (cycling ON) of the electrolyte pump during idle mode. Asdescribed above, deactivating the electrolyte pump may include turningoff the electrolyte pump, wherein the pump may remain dormant while theredox flow battery system may be maintained in a state (e.g., SOCgreater than a threshold SOC) where the redox flow battery system canreadily provide a desired power output promptly upon receiving a powerrequest. In other words, the first threshold duration may correspond toa pump OFF interval during idle mode. In one example, the firstthreshold duration may be a fixed interval relative to a pump ONinterval corresponding to a second threshold duration. In one case, thepump OFF interval may be set relative to the pump ON interval such thatan overall pump OFF duration during idle mode is 5/6 of an overallduration of idle mode; in other words, a ratio of the pump OFF intervalto the pump ON interval would be 5 to 1 and a ratio of the firstthreshold duration to the second threshold duration would be 5 to 1. Forexample, the first threshold duration may be equal to 50 minutes and thesecond threshold duration may be equal to 10 minutes; thus, during idlemode, the pump would remain OFF 50 minutes for every hour of idle time.

Alternatively, the first threshold duration may be adjusted based on apower module voltage measured prior to the initiation of the idle mode.In one example, the first threshold duration may be higher correspondingto the power module voltage just prior to entering idle mode beinghigher, and the first threshold duration may be lower for the case wherethe power module voltage just prior to entering idle mode is lower. Inthis way, the first threshold duration may allow for longer cyclingperiods from a higher initial voltage prior to entering idle mode, andmay allow for shorter cycling periods from a lower initial voltage priorto entering idle mode. For the case where the first timer is less thanthe first threshold duration, the method 400 proceeds from 410 to 412 tocontinue to monitor the first timer and maintain the electrolyte pumpdeactivated.

If the first timer is greater than or equal to the first thresholdduration, then the method 400 proceeds from 410 to 414 to send a controlsignal to the actuator of the electrolyte pump to activate theelectrolyte pump at an idle threshold flow rate. The idle threshold flowrate may correspond to an electrolyte flow rate below which idlingelectrolyte within the power module is not refreshed enough so that aresponsiveness of the redox flow battery system for supplying power ondemand to an external load is reduced below a desirable level. In otherwords, if the electrolyte flow rate is below the idle threshold flowrate, the supply of electrolyte to the redox flow battery cells may notbe sufficient to promptly respond to a command from the controller 88for supplying power to an external load. As such there may be anundesirable extended delay, allowing for enough fresh electrolyte toreach the redox flow battery cells, before enough current/power can besupplied to meet the commanded demand. Said in another way, if the pumpis not reactivated after the first threshold duration, a responsivenessof the redox flow battery system to promptly supply power to a commandedexternal load may be reduced. In one example, the idle threshold flowrate may be less than a charge or discharge threshold flow rate of theredox flow battery system (e.g., threshold flow rates during the batterycharge and discharge modes, respectively). For example, the idlethreshold flow rate may correspond to 10% of the charge or dischargethreshold flow rate. Accordingly, in such examples, the idle thresholdflow rate may be non-zero. Similar to examples wherein the deactivationthreshold flow rate is non-zero, the idle threshold flow rate beingnon-zero may help to preserve the life of the electrolyte pump, byavoiding completely shutting the pump off. In an additional oralternative example, the idle threshold flow rate may be greater than orequal to the deactivation threshold flow rate. In some instances, theidle threshold flow rate to a negative electrolyte chamber may bedifferent from the idle threshold flow rate to the positive electrolytechamber. At any rate, it will be appreciated that the pump flow rate isreduced for idle mode compared to the pump flow rate during the batterycharge and discharge modes. A third timer, timer 3, is initiated inconjunction with the activation of the electrolyte pump, the third timermeasuring a pump ON duration during the idle pump cycling of method 400.

In some examples, at least a negative electrode compartment of the redoxflow battery system is drained, resulting in partial to completereplacement of a volume of electrolyte stored in the negative electrodecompartment. In other examples, both the negative electrode compartmentand a positive electrode compartment are drained. The electrolytedrained from the electrode compartment(s) may be returned to acorresponding electrolyte storage tank or may be passed through anelectrolyte treatment system before delivery to the electrolyte storagetank. The electrode compartment(s) may be concurrently refilled from theelectrolyte storage tank during draining to maintain a steady stateelectrolyte volume in the electrode compartment(s) or the electrodecompartment(s) may be first partially drained and then refilledimmediately before or when the third timer reaches a second thresholdduration.

In some examples, the refilling of the electrode compartment(s) mayoccur periodically at either the negative electrode compartmentexclusively or both the negative and positive electrode compartments.For example, the electrode compartment(s) may be refilled for 5 minutesevery hour to maintain the redox flow battery system at a relativelywarm temperature.

At 416, following measurement of the third timer, the method 400includes determining if the third timer is greater than the secondthreshold duration. The second threshold duration may be based on anamount of time desired to activate the pump during the idle mode tomaintain a responsiveness of the redox flow battery system for meetinganticipated power demands from an external load, while also decreasingbattery capacity losses experienced by the redox flow battery system andparasitic power losses due to operation of the pump and heating element.Capacity losses may include a mitigated power output of the redox flowbattery system and may also include minimized ionic mixing at themembrane interface. In one example, the second threshold duration is 20%of the first threshold duration.

If the third timer is less than the second threshold duration, then theelectrolyte has not been adequately refreshed to achieve the desiredsystem responsiveness to an anticipated external load command, and themethod 400 proceeds from 416 to 418 to continue monitoring the thirdtimer. The electrolyte pump remains activated at the idling thresholdflow rate while the third timer is less than the second thresholdduration.

If the third timer is greater than or equal to the second thresholdduration at 416, indicating that the electrolyte has been refreshedenough to allow for achieving a desired system responsiveness to ananticipated external load command, method 400 continues to 420 where itdetermines if idle mode conditions are continued to be met. Meeting idlemode conditions may include determining if the redox flow battery systemis not in either a charging mode (e.g., the battery charge mode) or adischarging mode (e.g., the battery discharge mode). Thus, determiningif idle mode conditions are still met may be performed as described formethod 300. For the case where idle conditions are not met (e.g., thepower set point is greater or less than zero and the redox flow batterysystem enters the charging or discharging mode), the method 400 returnsto method 300 of FIG. 3 . For the case where idle conditions are stillmet, and following measurement of the second timer, the method 400continues to 422 to determine if the second timer is greater than athird threshold duration.

The third threshold duration may be a duration of time greater than thefirst threshold duration, beyond which a pH of the negative electrolytemay rise, leading to iron hydroxide (Fe(OH)₃) formation at the negativeelectrode. In some examples, the third threshold duration may be greaterthan the first threshold duration and the second threshold durationcombined. Furthermore, the third threshold duration may be longer thanthe combined first and second threshold durations so that the firsttimer may reset and cycle through the first and second thresholddurations one or more times before the third threshold duration elapses.

An increased presence of Fe(OH)₃ at the negative electrode compartmentmay degrade a performance of the redox flow battery system subsequent tothe redox flow battery system exiting the idle mode. As such, the thirdthreshold duration may be a period of time during which a likelihood ofFe(OH)₃ build-up to an extent that results in poor battery performanceis increased. In one example, the third threshold duration may be a setperiod of time, such as three hours, five hours, or eight hours. Inanother example, the third threshold duration may be based on the firstthreshold duration. For example, the third threshold duration may bethree times or five times the first threshold duration.

If the second timer does not reach or exceed the third thresholdduration, method 400 returns to 408 to continue idle mode operation. Inthis way, during the idle mode, method 400 repeatedly cycles theelectrolyte pump between the active state and the inactive state. Asdescribed above, each of the idle threshold temperature, deactivationthreshold flow rate, idle threshold flow rate, first threshold duration,second threshold duration, and third threshold duration may be adjustedaccording to the anticipated power demands during an idle mode. Forexample, when the anticipated power demands during an idle mode arehigher, an idle threshold temperature may be higher, a deactivationthreshold flow rate may be higher, an idle threshold flow rate may behigher, a first threshold duration may be lower, and a second thresholdduration may be higher in order to increase a responsiveness of theredox flow battery system. Conversely, when the anticipated powerdemands during an idle mode are lower, an idle threshold temperature maybe lower, a deactivation threshold flow rate may be lower, an idlethreshold flow rate may be lower, a first threshold duration may behigher, and a second threshold duration may be lower in order todecrease a responsiveness of the redox flow battery system whilereducing parasitic power losses due to pumping and heating and reducingshunt losses through the electrolyte. In this way, idle mode operationparameters may be adjusted by the controller 88 depending on theanticipated power needs to maintain a redox flow battery systemresponsiveness while reducing parasitic and shunting losses.

If the second timer is equal to or greater than the third thresholdduration, method 400 proceeds to method 500, as shown in FIG. 5 . Insome instances, the first timer may reach the first threshold durationconcurrent with the second timer reaching the third threshold duration.In such instances, method 500 may be prioritized over method 400 [e.g.,method 400 may proceed to method 500 at 410, rather than at 422, anddraining, purging, and refilling of the electrode compartment(s) may beprioritized over activation of the electrolyte pump]. At 502, method 500includes draining one or more electrode compartments of the redox flowbattery system. In some examples, only the negative electrodecompartment may be drained and the positive electrode compartment may beleft filled. For example, the negative and positive electrolytes in theelectrode compartments may be pumped out of the electrode compartmentsto an electrolyte storage tank of the redox flow battery system, such asthe integrated multi-chambered electrolyte storage tank 110 shown inFIG. 1 . Alternatively, the electrolyte may be treated at an electrolytetreatment system, such as one or more rebalancing reactors, forrestoring electrolyte charge balance and pH, before returning theelectrolyte to the electrolyte storage tank.

The emptied electrode compartment(s) may be flushed with a gas under anoxygen-free environment. As an example, the gas may be hydrogen or argonand delivered from a gas storage tank, such as the gas storage tank 102of FIG. 1 . The electrode compartments may be purged with gas for apredetermined period of time. The predetermined period of time may be anamount of time calculated based on a volume of the electrodecompartment(s) and a flow rate of gas to flush the electrodecompartment(s) with a volume of gas equal to a minimum multiple of thevolume of the electrode compartment(s). For example, the period of timemay be set to flush the electrode compartments with a volume of gas atleast once, double, triple, or five times the volume of the electrodecompartment(s). Alternatively, a pressure tester may be used todetermine if standing liquid hydraulic pressure is present.

The electrode compartment(s) are refilled with electrolyte at 506.Negative electrolyte may be pumped to the negative electrode compartmentand positive electrolyte may be pumped to the positive electrodecompartment from the electrolyte storage tank. Alternatively,electrolyte may be returned to the electrode compartment(s) from theelectrolyte treatment system, e.g., the one or more rebalancingreactors.

Upon refilling the electrode compartments with electrolyte, method 500includes determining if the idle mode conditions are still met at 508.Meeting idle mode conditions may include determining if the redox flowbattery system is not in either a charging mode or a discharging mode.Thus, determining if idle mode conditions are still met may be performedas described for method 300. If idle conditions are not met (e.g., theredox flow battery system enters charging or discharging mode), method500 returns to method 300 to determine current operating parameters ofthe redox flow battery system. If idle conditions are met, method 500returns to 408 of method 400 to continue monitoring timers 1 and 2.

By monitoring the first and second timers and carrying out processesdescribed in methods 300, 400, and 500, a loss of battery performanceand capacitance during periods when the redox flow battery system isidling may be mitigated. In some examples, method 400 may be excludedand the method 300 may proceed only to method 500 when the batteryenters the idle mode. Method 500, e.g., draining and purging theelectrode compartment(s), may provide more effective maintenance ofbattery performance than method 400, e.g., electrolyte pumping at higherfrequency, alone. As an example, method 400 may, in some instances, leadto shunting loss in larger battery modules when the redox flow batterysystem is in the idle mode for long periods, such as several hours ordays. Shunting losses, however, may be mitigated by draining and purgingthe electrode compartment(s). By draining and purging the electrodecompartment(s), followed by refilling with fresh electrolyte, thebattery capacitance may be restored, thereby minimizing losses due toshunting.

Turning now to FIG. 6 , it shows a time plot 600 graphicallyillustrating redox flow battery conditions during and outside of an idlemode with time measured along a horizontal axis, where time increasesfrom a left to right side of the time plot 600. The time plot 600illustrates the methods 300, 400, and 500 executed in parallel by thebattery system of FIGS. 1 and 2 . In this way, each of the methods 300,400, and 500 may occur simultaneous to one another. Plot 602 illustratesan electrolyte pump status, plot 604 illustrates if a redox flow batteryidle condition is being met, plot 606 illustrates a position of a drainvalve of one or more electrode compartments, and plot 608 illustratespassive gas flow (e.g., hydrogen or argon) into the one or moreelectrode compartments, as measured by, for example, a mass flowcontroller in a gas line coupling a gas cylinder or a head space of anelectrolyte storage tank to the one or more electrode compartments. Thepassive gas flow at plot 608 may be driven by a pressure gradient, e.g.,a difference in pressure between a gas storage tank and the one or moreelectrode compartments.

Prior to t1, the electrolyte pump is on (plot 602) and battery idleconditions are not met as shown by plot 604. The drain valve,controlling flow of electrolyte out of the one or more electrodecompartments and to an electrolyte treatment system, is closed (plot606) and gas is not flowing to the one or more electrode compartments(plot 608). As such, the battery may be in a charge or discharge mode.

At t1, redox flow battery idle conditions are met and the redox flowbattery transitions from the charge or discharge mode to the idle mode.The electrolyte pump is turned off in response to the transition to theidle mode. The drain valve is maintained closed and the gas is notflowing. One or more timers, e.g., the first and second timers describedin method 400 of FIG. 4 may also be initiated in response to adjustmentof the redox flow battery to the idle mode.

The first timer reaches a first threshold duration at t2. In response tothe first threshold duration elapsing, the electrolyte pump is actuatedon. A third timer may be activated. Electrolyte is thereby delivered tothe one or more electrode compartments.

At t3, the third timer reaches a second threshold duration. Theelectrolyte pump is deactivated and the drain valve is opened to allowat least a portion of the electrolyte in the one or more electrodecompartments to flow out. Pressure in the one or more electrodecompartments decreases, forming a vacuum, as electrolyte is drained out,compelling gas to flow into the one or more electrode compartments toalleviate the pressure gradient. When a desired amount of electrolyte isdrained from the one or more electrode compartments, determined based onan amount of time elapsed or a hydraulic pressure measurement from apressure tester, the drain valve is closed. Closing the drain valve alsohalts gas flow into the one or more electrode compartments.

A fourth threshold duration is reached at t4. At t4, the electrolytepump is activated to refill the one or more electrode compartments withfresh electrolyte. Accordingly, in one example, the electrolyte isdrained from the one or more electrode compartments, the one or moreelectrode compartments is purged with gas, and the one or more electrodecompartments is refilled with the fresh electrolyte in sequence.Refilling of the electrode compartments continues until a target volumeof electrolyte in the one or more electrode compartments is attained att5. The pump is deactivated at t5 and the redox flow battery remains inthe idle mode.

At t6, redox flow battery idle conditions are no longer met. As such,the electrolyte pump is reactivated with the drain valve closed. In thisway, the redox flow battery is in the charge or discharge mode and hasexited the idle mode.

Graph 700 is shown in FIG. 7 , plotting percent battery SOC, along thex-axis, against time in seconds, along the y-axis. Three idle modetreatments are depicted in graph 700, including plot 702 illustratingelectrolyte pumping cycling for 30 minutes with a 30-minute drain, plot704 illustrating electrolyte pumping cycling for 45 minutes with a15-minute drain, and plot 706 illustrating complete drainage ofelectrolyte in the electrode compartments. The 30-minute and 15-minutedrainages of the electrode compartments resulted in only partial removaland replacement of electrolyte while complete drainage demanded aprolonged period of time, as indicated at arrow 708.

Both plots 702 and 704 show a gradual decrease in battery SOC over time,including multiple pumping and partial drainage cycles. A single fulldrainage cycle is shown by plot 706. Upon refilling the electrodecompartments at arrow 708, the SOC may return to a percentage similar toan initial SOC of the battery. In one example, as shown in FIG. 7 , thebattery SOC may initially be 48% and may return to 47.8% after completedrainage. In contrast, both plots 702 and 704 show reduced battery SOCat a time period indicated by arrow 708.

In this way, battery performance may be maintained even when a redoxflow battery is operated in an idle mode for an extended period of time.Upon fully draining at least a negative electrode compartment of theredox flow battery upon passage of a threshold period of time, adverseeffects of idle mode operation, such as formation of Fe(OH)₃ and rise inelectrolyte pH, may be mitigated. The complete drainage of the electrodecompartment(s) may be combined with periodic, shorter term electrolytepumping. The electrolyte pumping may be accompanied by at least partialdrainage of electrolyte from the electrode compartment(s). By fullyreplacing the electrolyte in the electrode compartment(s), a performanceof the redox flow battery may be maintained for a longer period of time,thereby prolonging a useful life of the battery.

The disclosure also provides support for a method of operating a redoxflow battery system, the method comprising: responsive to switching theredox flow battery system to an idle mode, wherein the idle modeincludes operation of the redox flow battery system outside of acharging mode and outside of a discharging mode, completely drainingelectrolytes from one or more electrode compartments of the redox flowbattery system, purging the one or more electrode compartments with agas, and refilling the one or more electrode compartments with freshelectrolytes. In a first example of the method, the method furtherincludes wherein the electrolytes are completely drained from the one ormore electrode compartments responsive to a first threshold period oftime elapsing, and wherein the method further comprises, in response toa second threshold period of time elapsing while the redox flow batterysystem is in the idle mode, the second threshold period of time beingshorter than the first threshold period of time, activating anelectrolyte pump to circulate the electrolytes through the one or moreelectrode compartments. In a second example of the method, optionallyincluding the first example of the method, the method further comprisesdeactivating the electrolyte pump following activation of theelectrolyte pump (e.g., when a third threshold period of time elapses,the third threshold period of time initiated upon activation of theelectrolyte pump). In a third example of the method, optionallyincluding one or more of the first and second examples of the method,the method further includes wherein purging the one or more electrodecompartments with the gas comprises flushing the one or more electrodecompartments with an inert gas. In a fourth example of the method,optionally including the first through third examples, purging the oneor more electrode compartments with the gas comprises flushing the emptyone or more electrode compartments for a pre-set period of time. In afifth example of the method, optionally including one or more of thefirst through fourth examples of the method, the method further includeswherein purging the one or more electrode compartments with the gascomprises flowing the gas to the one or more electrode compartmentsduring draining of the one or more electrode compartments until apressure measured in the one or more electrode compartments indicatesthat the one or more electrode compartments are empty. In a sixthexample of the method, optionally including one or more of the firstthrough fifth examples of the method, the method further includeswherein completely draining the electrolytes from the one or moreelectrode compartments, purging the one or more electrode compartments,and refilling the one or more electrode compartments comprises draining,purging, and refilling a negative electrode compartment. In a seventhexample of the method, optionally including one or more of the firstthrough sixth examples of the method, the method further includeswherein completely draining the electrolytes from the one or moreelectrode compartments, purging the one or more electrode compartments,and refilling the one or more electrode compartments comprises draining,purging, and refilling each of a negative electrode compartment and apositive electrode compartment. In an eighth example of the method,optionally including one or more of the first through seventh examplesof the method, the method further includes wherein refilling the one ormore electrode compartments with the fresh electrolytes comprisesreplenishing the one or more electrode compartments with electrolyteshaving a lower pH and a lower iron hydroxide content than theelectrolytes drained from the one or more electrode compartments. In aninth example of the method, optionally including one or more of thefirst through eighth examples of the method, the method further includeswherein completely draining the electrolytes from the one or moreelectrode compartments, purging the one or more electrode compartmentswith the gas, and refilling the one or more electrode compartments withthe fresh electrolytes are performed in sequence, and wherein refillingthe one or more electrode compartments with the fresh electrolytesoccurs periodically.

The disclosure also provides support for a method of operating a redoxflow battery system, the method comprising: switching the redox flowbattery system to an idle mode, wherein the idle mode includes operationof the redox flow battery system outside of a charging mode and outsideof a discharging mode, responsive to a first threshold period of timeelapsing while the redox flow battery system is in the idle mode,activating an electrolyte pump to circulate electrolyte through at leastone electrode compartment of the redox flow battery system (e.g., for apre-set duration), and responsive to a second threshold period of timeelapsing while the redox flow battery system is in the idle mode, thesecond threshold period of time longer than the first threshold periodof time, completely draining the at least one electrode compartment,purging the at least one electrode compartment with a gas, andperiodically refilling the at least one electrode compartment with freshelectrolyte. In a first example of the method, the method furthercomprises initiating a first timer to monitor passage of time relativeto the first threshold period of time and a second timer to monitorpassage of time relative to the second threshold period of time, whereinthe first timer and the second timer are simultaneously initiated byswitching of the redox flow battery system to the idle mode. In a secondexample of the method, optionally including the first example of themethod, the method further comprises upon activating the electrolytepump, initiating a third timer to monitor passage of time relative to athird threshold period of time, and deactivating the electrolyte pumpafter passage of the third threshold period of time. In a third exampleof the method, optionally including one or more of the first and secondexamples of the method, the method further includes wherein elapsing ofthe first and third threshold periods of time occur before the secondthreshold period of time elapses, and wherein the first timer is resetwhen the third threshold period of time elapses. In a fourth example ofthe method, optionally including one or more of the first through thirdexamples of the method, the method further includes wherein activatingthe electrolyte pump in response to the first threshold period of timeelapsing occurs one or more times during the second threshold period oftime. In a fifth example of the method, optionally including one or moreof the first through fourth examples of the method, the method furthercomprises prioritizing draining, purging, and periodically refilling theat least one electrode compartment in response to the second thresholdperiod of time elapsing over activating the electrolyte pump in responseto the first threshold period of time elapsing when elapsing of thefirst and second threshold periods of time coincide. In a sixth exampleof the method, optionally including one or more of the first throughfifth examples of the method, the method further includes whereinpurging the at least one electrode compartment with the gas comprisesflowing the gas through the at least one electrode compartment underoxygen-free conditions (e.g., for a duration of time) to flush the atleast one electrode compartment with a target volume of the gas andwherein the at least one electrode compartment comprises a negativeelectrode compartment and a positive electrode compartment. In a seventhexample of the method, optionally including one or more of the firstthrough sixth examples of the method, the method further compriseshalting the flow of the gas through the at least one electrodecompartment and periodically refilling the at least one electrodecompartment when the target volume of the gas is attained.

The disclosure also provides support for a redox flow battery system,comprising: a power module comprising a plurality of redox flow batterycell stacks, each of the plurality of redox flow battery cell stackscomprising a redox flow battery cell, an electrolyte pump capable ofdelivering electrolyte from an electrolyte tank to the power module, anda power control system with a controller storing executable instructionsin non-transitory memory, the instructions executable to: switch theredox flow battery system to an idle mode, wherein the idle modeincludes operation of the redox flow battery system outside of acharging mode and outside of a discharging mode, activate theelectrolyte pump while the redox flow battery system is in the idle modeto circulate the electrolyte through one or more electrode compartmentsof the redox flow battery system (e.g., for a pre-set duration when afirst threshold period of time elapses), completely drain theelectrolyte from the one or more electrode compartments of the redoxflow battery system while the redox flow battery system in in the idlemode (e.g., when a second threshold period of time elapses), purge thedrained one or more electrode compartments with a gas, and periodicallyrefill the drained and purged one or more electrode compartments withfresh electrolyte. In a first example of the redox flow battery system,the redox flow battery system further includes wherein completelydraining the electrolyte from the one or more electrode compartmentscomprises opening a drain valve of each of the one or more electrodecompartments (e.g., in response to the second threshold period of timeelapsing). In a second example of the redox flow battery system,optionally including the first example of the redox flow battery system,the redox flow battery system further includes wherein the drain valveis closed when the one or more electrode compartments are flushed with atarget volume of the gas, and wherein the gas is hydrogen or argon.

The following claims particularly point out certain combinations andsub-combinations regarded as novel and non-obvious. These claims mayrefer to “an” element or “a first” element or the equivalent thereof.Such claims should be understood to include incorporation of one or moresuch elements, neither requiring nor excluding two or more suchelements. Other combinations and sub-combinations of the disclosedfeatures, functions, elements, and/or properties may be claimed throughamendment of the present claims or through presentation of new claims inthis or a related application. Such claims, whether broader, narrower,equal, or different in scope to the original claims, also are regardedas included within the subject matter of the present disclosure.

1. A method of operating a redox flow battery system, the methodcomprising: responsive to switching the redox flow battery system to anidle mode, wherein the idle mode includes operation of the redox flowbattery system outside of a charging mode and outside of a dischargingmode, initiating an off cycle timer monitoring an off cycle thresholdperiod of time; activating an electrolyte pump in response to elapsingof the off cycle threshold period of time to circulate electrolytesthrough one or more electrode compartments.
 2. The method of claim 1,wherein a drain timer is initiated concurrent with the off cycle timerand an on cycle timer is initiated after the off cycle threshold periodof time elapses, and wherein the on cycle timer measures an on cyclethreshold period of time for circulating the electrolytes and the draintimer monitors a drain threshold period of time.
 3. The method of claim2, wherein the drain threshold period of time is longer than the offcycle threshold period of time.
 4. The method of claim 2, furthercomprising completely draining electrolytes from one or more electrodecompartments of the redox flow battery system, purging the one or moreelectrode compartments with a gas, and refilling the one or moreelectrode compartments with fresh electrolytes when the drain thresholdperiod of time elapses.
 5. The method of claim 4, wherein a vacuum isgenerated in the one or more electrode compartments when the one or moreelectrode compartments are drained, and wherein the vacuum draws the gasinto the one or more electrode compartments to purge the one or moreelectrode compartments.
 6. The method of claim 4, wherein when elapsingof the off cycle threshold period of time is concurrent with elapsing ofthe drain threshold period of time, the draining of the electrolytesfrom the one or more electrode compartments is prioritized overactivation of the electrolyte pump.
 7. The method of claim 4, furthercomprising, in response to maintaining the redox flow battery system inthe idle mode after the drain threshold period of time has elapsed andthe one or more electrode compartments are refilled with the freshelectrolytes, initiating the off cycle timer again.
 8. The method ofclaim 4, wherein the electrolytes are drained from the one or moreelectrode compartments by opening a drain valve of the one or moreelectrode compartments.
 9. The method of claim 8, wherein the drainvalve is closed when the one or more electrode compartments are purgedwith the gas, and wherein the gas is hydrogen or argon.
 10. A method fora redox flow battery system, comprising: responsive to operation of theredox flow battery system in an idle mode, cycling an electrolyte pumpbetween an off interval and an on interval, the off interval having aduration corresponding to an off threshold period of time and the oninterval having a duration corresponding to an on threshold period oftime, wherein electrolytes are circulated through one or more electrodecompartments during the on interval.
 11. The method of claim 10, whereinthe off threshold period of time is longer than the on threshold periodof time.
 12. The method of claim 10, wherein the off threshold period oftime is adjusted based on a power module voltage of the redox flowbattery system, and wherein the off threshold period of time isincreased when the power module voltage is increased and decreased whenthe power module voltage is decreased.
 13. The method of claim 10,wherein the electrolytes are circulated through the one or moreelectrode compartments during the on interval at an idle threshold flowrate, and wherein the idle threshold flow rate is lower than a charge ordischarge threshold flow rate.
 14. The method of claim 10, wherein theduration of the off threshold period of time is decreased whenanticipated power demands are increased and the duration of the offthreshold period of time is increased when the anticipated power demandsare decreased.
 15. The method of claim 10, further comprising monitoringa drain threshold period of time, the drain threshold period of timeinitiated concurrently with initiation of the off threshold period oftime, and wherein when the drain threshold period of time elapses, theone or more electrode compartments are drained, purged, and refilled.16. The method of claim 15, wherein the drain threshold period of timeis longer than the off threshold period of time.
 17. The method of claim15, wherein the drain threshold period of time is longer than the offthreshold period of time and the on threshold period of time combined.18. The method of claim 15, wherein the drain threshold period of timeis a duration of time before a pH of the electrolytes in the one or moreelectrode compartments rises and causes formation of iron hydroxide. 19.The method of claim 15, wherein the drain threshold period of time is aduration of time where a likelihood of reduced battery performance isincreased due to accumulation of iron hydroxide.
 20. The method of claim15, wherein the one or more electrode compartments are refilled with theelectrolytes from an electrolyte storage tank or at least onerebalancing reactor.